CN110785894A - Electric wire connection structure - Google Patents
Electric wire connection structure Download PDFInfo
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- CN110785894A CN110785894A CN201880042148.8A CN201880042148A CN110785894A CN 110785894 A CN110785894 A CN 110785894A CN 201880042148 A CN201880042148 A CN 201880042148A CN 110785894 A CN110785894 A CN 110785894A
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- copper
- aluminum
- based conductor
- conductor
- coated
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/02—Soldered or welded connections
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/58—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation characterised by the form or material of the contacting members
- H01R4/62—Connections between conductors of different materials; Connections between or with aluminium or steel-core aluminium conductors
- H01R4/625—Soldered or welded connections
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/06—Soldering, e.g. brazing, or unsoldering making use of vibrations, e.g. supersonic vibrations
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
- H01R43/02—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for soldered or welded connections
- H01R43/0207—Ultrasonic-, H.F.-, cold- or impact welding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
- H01R43/04—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for forming connections by deformation, e.g. crimping tool
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/32—Wires
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/70—Insulation of connections
- H01R4/72—Insulation of connections using a heat shrinking insulating sleeve
Abstract
The invention provides an electric wire connection structure which effectively inhibits the increase of resistance and the reduction of joint strength (pull strength) caused by gap corrosion of an ultrasonic joint formed by a copper-based conductor exposed part and an aluminum-based conductor exposed part. The wire connection structure (1) comprises 1 or more copper-based conductor-coated wires (10) each having a copper-based conductor-coated portion (11) and an exposed portion (12), and 1 or more aluminum-based conductor-coated wires (20) each having an aluminum-based conductor-coated portion (21) and an exposed portion (22), an ultrasonic joint (30) is formed at a conductor lamination portion where a copper-based conductor exposure portion (12) and an aluminum-based conductor exposure portion (22) are overlapped, and a joint interface (33) of the ultrasonic joint (30) is observed in a cross section, the total contact length L, which is the sum of the lengths of the portions of the copper-based conductor exposed portions (12) that are in contact with the aluminum-based conductor exposed portions (22), and the total x, which is the contour length of the space S formed by the portions of the copper-based conductor exposed portions (12) that are separated from the aluminum-based conductor exposed portions (22), satisfy the relational expression of (x/L) × 100 ≦ 10%.
Description
Technical Field
The invention provides a wire connection structure having an ultrasonic bonding portion formed by a copper-based conductor exposed portion and an aluminum-based conductor exposed portion.
Background
As the electric wire connecting structure formed by electrically connecting electric wires to each other, for example, a wire harness arranged in an automobile to supply power or transmit a signal is cited. Some wire harnesses are very long, and when power is supplied to each device from one power supply, for example, the number of wires increases and the weight increases because the wires are wired one by one from one power supply. Therefore, the following method may be used: in general, from the viewpoint of weight reduction, the electric wires arranged between the position of connection with the power supply and the position close to each device (near position) are formed with 1 thick wire, and are branched into a plurality of thin wires using a joint after approaching each device, and a light-weight aluminum-based material is used instead of a copper-based material as a conductor constituting the electric wires.
As a bonding method, for example, there is a so-called resistance welding method in which a portion to be welded is sandwiched between 2 electrodes to flow a current, and metals are bonded to each other by heat generation of resistance and a pressing force.
In the resistance welding method, if the conductive metals of the wires to be joined are all copper-based materials, it is relatively easy to form a sound joint, but when dissimilar metals such as an Al-based conductor and a Cu-based conductor are joined to each other, only the Al conductor having a low melting point melts, but the Cu conductor having a high melting point does not melt, so that a sound joint cannot be formed.
Therefore, when joining dissimilar metals to each other, an ultrasonic joining method capable of joining at normal temperature is generally used. For example, patent document 1 describes a wire harness in which wires constituting a conductor of an insulated wire and wires are joined to a metal sleeve (or a metal foil or the like).
In addition, from the viewpoint of reducing the number of members constituting the wire harness, it is assumed that the ultrasonic bonding is directly performed in a state where the copper-based conductor and the aluminum-based conductor are overlapped without using the metal sleeve.
However, when the copper-based conductor and the aluminum-based conductor are superposed and ultrasonically bonded, the copper-based conductor and the aluminum-based conductor have the following problems: in some cases, a defective portion (space) where the copper-based conductor and the aluminum-based conductor constituting the ultrasonic bonding portion are not bonded (contacted) easily exists at the bonding interface therebetween due to a combination of different conductor materials, a change in bonding conditions, or the like, and in this case, the aluminum-based conductor portion is anodized due to interstitial corrosion, and thus resistance is increased and bonding strength (pull strength) is easily lowered.
Documents of the prior art
Patent document
[ patent document 1] Japanese patent application laid-open No. 2010-44887
Disclosure of Invention
[ problems to be solved by the invention ]
Accordingly, an object of the present invention is to provide a wire connection structure in which the properties of the joint interface of the ultrasonic joint formed by the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are optimized, and thereby the increase in electrical resistance and the decrease in joint strength (pull strength) due to the interstitial corrosion are effectively suppressed.
[ means for solving the problems ]
The present inventors have conducted intensive studies on the above problems, and as a result, have found that the following means are provided to complete the present invention: in forming the ultrasonic joint by the copper-based conductor exposed portion and the aluminum-based conductor exposed portion, it is preferable that one of the copper-based conductor exposed portion and the aluminum-based conductor exposed portion is made of a material that is more easily deformed than the other, and the copper-based conductor and the aluminum-based conductor are made of a combination of conductors formed of a material having a difference in tensile strength of 100MPa or more, so that one of the conductor exposed portions is relatively largely collapsed by a pressure force at the time of ultrasonic joint and is easily plastically fluidized, and therefore, in a non-joint (non-contact) space that is easily formed between the copper-based conductor exposed portion and the aluminum-based conductor exposed portion constituting the joint interface, one of the conductor exposed portions enters by plastic fluidization to fill the space, and as a result, an ultrasonic joint having a sound joint interface can be formed, and an increase in electrical resistance due to gap corrosion can be effectively suppressed, and, Or the joint strength (tensile strength) is decreased.
That is, the main configuration of the present invention is as follows.
(1) An electric wire connection structure comprising: 1 or more copper-based conductor-coated electric wires each having a copper-based conductor-coated portion in which a copper-based conductor made of copper or a copper alloy is coated with an insulating coating, and a copper-based conductor-exposed portion in which a part of the insulating coating is stripped to a predetermined length to expose the copper-based conductor; and 1 or more aluminum conductor-coated wires each having an aluminum conductor-coated portion in which an aluminum conductor made of aluminum or an aluminum alloy is covered with an insulating coating, and an aluminum conductor-exposed portion in which a part of the insulating coating is stripped off by a predetermined length to expose the aluminum conductor; and an electric wire connection structure in which a joint portion is formed at a conductor laminated portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are overlapped, wherein a joint interface of the joint portion is formed so that the aluminum-based conductor-coated electric wire is melted to fill a gap of the copper-based conductor-coated electric wire in a cross-sectional view.
(2) An electric wire connection structure comprising: 1 or more copper-based conductor-coated electric wires each having a copper-based conductor-coated portion in which a copper-based conductor made of copper or a copper alloy is coated with an insulating coating, and a copper-based conductor-exposed portion in which a part of the insulating coating is stripped to a predetermined length to expose the copper-based conductor; and 1 or more aluminum conductor-coated electric wires each having an aluminum conductor-coated portion in which an aluminum conductor made of aluminum or an aluminum alloy is coated with an insulating coating, and an aluminum conductor-exposed portion in which a part of the insulating coating is stripped off by a predetermined length to expose the aluminum conductor; and an electric wire connection structure in which an ultrasonic joint is formed at a conductor laminated portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion overlap, wherein, in a cross-sectional view of a joint interface of the ultrasonic joint, a total contact length, which is a total length of a portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are in contact with each other, is L, and a total length of a contour line of a space formed at a portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are separated from each other is x, the following relational expression is satisfied: (x/L) x 100 is less than or equal to 10 percent.
(3) The electric wire connection structure according to the above (1) or (2), wherein a difference in tensile strength between the copper-based conductor and the aluminum-based conductor is 100MPa or more.
(4) The electric wire connection structure according to any one of the above (1) to (3), characterized by further having a joint pipe in which the ultrasonic bonding portion is formed on an outer peripheral side of the conductor laminated portion.
[ Effect of the invention ]
According to the present invention, there is provided an electric wire connection structure including: 1 or more copper-based conductor-coated electric wires each having a copper-based conductor-coated portion in which a copper-based conductor made of copper or a copper alloy is coated with an insulating coating, and a copper-based conductor-exposed portion in which a part of the insulating coating is stripped to a predetermined length to expose the copper-based conductor; and 1 or more aluminum conductor-coated electric wires each having an aluminum conductor-coated portion in which an aluminum conductor made of aluminum or an aluminum alloy is coated with an insulating coating, and an aluminum conductor-exposed portion in which a part of the insulating coating is stripped off by a predetermined length to expose the aluminum conductor; and a wire connection structure in which a joint portion is formed at a conductor laminated portion in which the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are overlapped, wherein a joint interface of the joint portion is formed such that the aluminum-based conductor-coated wire is melted to fill a gap of the copper-based conductor-coated wire in a cross-sectional view, thereby effectively suppressing an increase in resistance and a decrease in joint strength (tensile strength) due to corrosion of the gap.
Further, according to the present invention, there is provided an electric wire connection structure including: 1 or more copper-based conductor-coated electric wires each having a copper-based conductor-coated portion in which a copper-based conductor made of copper or a copper alloy is coated with an insulating coating, and a copper-based conductor-exposed portion in which a part of the insulating coating is stripped to a predetermined length to expose the copper-based conductor; and 1 or more aluminum conductor-coated wires each having an aluminum conductor-coated portion in which an aluminum conductor made of aluminum or an aluminum alloy is covered with an insulating coating, and an aluminum conductor-exposed portion in which a part of the insulating coating is stripped off by a predetermined length to expose the aluminum conductor; and an electric wire connection structure in which an ultrasonic joint is formed at a conductor laminated portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion overlap, wherein, in a cross-sectional view of a joint interface of the ultrasonic joint, a total contact length, which is a total length of a portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are in contact with each other, is L, and a total length of a contour line of a space formed at a portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are separated from each other is x, the following relational expression is satisfied: (x/L). times.100. ltoreq.10%, thereby effectively suppressing an increase in electrical resistance or a decrease in joint strength (tensile strength) due to interstitial corrosion.
Drawings
Fig. 1 is a perspective view of a wire connection structure according to an embodiment of the present invention.
Fig. 2 is a cross-sectional photograph of an ultrasonic bonding section constituting a wire connection structure according to another embodiment of the present invention.
Fig. 3 is a view showing the ultrasonic bonding portion of fig. 2 by lines.
Fig. 4 is a diagram showing, in solid lines, a portion where two exposed portions come into contact (joined) at a joining interface between an aluminum-based conductor exposed portion and a copper-based conductor exposed portion constituting the ultrasonic joining portion of fig. 3.
Fig. 5 is a solid line view showing a space formed by a portion where two exposed portions are separated, which exists at a bonding interface between an aluminum-based conductor exposed portion and a copper-based conductor exposed portion constituting the ultrasonic bonding portion of fig. 3.
Fig. 6 is a diagram for explaining a method of measuring the total x of the total contact length L of the contact portion shown in fig. 4 and the contour line length of the space shown in fig. 5.
Fig. 7 is a schematic view for explaining a process of overlapping the copper-based conductor exposed portion and the aluminum-based conductor exposed portion and performing ultrasonic bonding using an ultrasonic bonding apparatus.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. Fig. 1 is a perspective view of a wire connection structure according to an embodiment of the present invention. The wire connection structure 1 shown in the drawings has: 1 or more copper-based conductor-coated electric wires 10 having copper-based conductor-coated portions 11 and copper-based conductor-exposed portions 12, and 1 or more aluminum-based conductor-coated electric wires 20 having aluminum-based conductor-coated portions 21 and aluminum-based conductor-exposed portions 22. The wire connection structure 1 further includes an ultrasonic bonding portion 30 formed in a conductor lamination portion where the copper-based conductor exposure portion 12 and the aluminum-based conductor exposure portion 22 overlap.
(electric wire connecting structure)
The wire connection structure 1 of the present invention includes: 1 or more copper conductor-coated electric wires 10, each of the copper conductor-coated electric wires 10 having a copper conductor-coated portion 11 in which a copper conductor made of copper or a copper alloy is coated with an insulating coating, and a copper conductor-exposed portion 12 in which a part of the insulating coating is stripped to a predetermined length to expose the copper conductor; and 1 or more aluminum conductor-coated electric wires 20, each of the aluminum conductor-coated electric wires 20 having an aluminum conductor-coated portion 21 in which an aluminum conductor made of aluminum or an aluminum alloy is covered with an insulating coating, and an aluminum conductor-exposed portion 22 in which a portion of the insulating coating is stripped off by a predetermined length to expose the aluminum conductor; and a wire connection structure in which a joint portion is formed at a conductor laminated portion where the copper-based conductor exposure portion and the aluminum-based conductor exposure portion overlap, wherein a joint interface of the joint portion is formed so that the aluminum-based conductor-coated wire melts and fills a gap of the copper-based conductor-coated wire in a cross-sectional view.
The wire connection structure 1 of the present invention includes: 1 or more copper conductor-coated electric wires 10, each of the copper conductor-coated electric wires 10 having a copper conductor-coated portion 11 in which a copper conductor made of copper or a copper alloy is coated with an insulating coating, and a copper conductor-exposed portion 12 in which a part of the insulating coating is stripped to a predetermined length to expose the copper conductor; and 1 or more aluminum conductor-coated electric wires 20, each of the aluminum conductor-coated electric wires 20 having an aluminum conductor-coated portion 21 in which an aluminum conductor made of aluminum or an aluminum alloy is covered with an insulating coating, and an aluminum conductor-exposed portion 22 in which a portion of the insulating coating is stripped off by a predetermined length to expose the aluminum conductor; and an electric wire connection structure in which an ultrasonic joint is formed in a conductor laminated portion where a copper-based conductor exposure portion and an aluminum-based conductor exposure portion overlap, wherein, in a cross-sectional view of a joint interface of the ultrasonic joint, when a total contact length, which is a total length of a portion where the copper-based conductor exposure portion and the aluminum-based conductor exposure portion are in contact with each other, is L, and a total length of a contour line of a space formed in a portion where the copper-based conductor exposure portion and the aluminum-based conductor exposure portion are separated from each other is x, the following relational expression is satisfied: (x/L) x 100 is less than or equal to 10 percent. As described below, the wire connection structure 10 can effectively suppress an increase in electrical resistance and a decrease in bonding strength (pull strength) due to crevice corrosion.
(copper conductor-coated electric wire)
The copper-based conductor-coated electric wire 10 used in the present invention includes a copper-based conductor-coated portion 11 in which a copper-based conductor made of copper or a copper alloy is coated with an insulating coating, and a copper-based conductor-exposed portion 12 in which a part of the insulating coating is stripped to a predetermined length to expose the copper-based conductor. The copper-based conductor covered electric wire 10 may be, for example, 1 covered electric wire in which a copper-based conductor formed by bundling a plurality of strands made of a copper-based material is covered with an insulating coating, or may be a plurality of covered electric wires in which such covered electric wires are bundled. The copper-based conductor is preferably formed by twisting a strand so as to have a predetermined cross-sectional area, but is not limited to this form and may be formed of a single wire. The wire diameter and number of wires constituting the copper-based conductor are not particularly limited, but for example, the wire diameter of the wire is preferably in the range of 0.05 to 1mm, and the number of wires is preferably in the range of 7 to 90.
The copper-based conductor is not particularly limited, and examples thereof include pure copper such as tough pitch copper, oxygen-free copper, and phosphorus deoxidized copper, and brass, phosphor bronze, corson-based copper alloy (Cu — Ni — Si-based alloy).
As such copper or copper alloy, for example, JIS H3100: 2012 pure copper of alloy No. C1000 series, Cu — Zn alloy of alloy No. C2000 series, Cu — Sn alloy of alloy No. C5000 series, and Cu — Al alloy of alloy No. C6000 series.
The insulating coating is not particularly limited as long as it is a material having insulating properties, and examples thereof include a halogen-based resin containing polyvinyl chloride, crosslinked polyvinyl chloride, chloroprene rubber, or the like as a main component, and a halogen-free resin containing polyethylene, crosslinked polyethylene, ethylene-propylene rubber, silicone rubber, polyester, or the like as a main component, and particularly a polyvinyl chloride resin is used as a resin material constituting the insulating coating. Further, additives such as a plasticizer and a flame retardant may be contained in these resin materials as needed.
The copper-based conductor coating portion 11 represents a portion of the copper-based conductor coated with the insulating coating, which does not expose the copper-based conductor, in the copper-based conductor coated electric wire 10 in which the copper-based conductor is covered with the insulating coating. The copper-based conductor coating portion 11 is the first portion of the copper-based conductor that is not affected by the ultrasonic wave described later.
The copper-based conductor exposure portion 12 is a portion where a copper-based conductor is exposed by stripping a portion of the insulating coating by a predetermined length. The copper-based conductor exposure portion 12 is a portion of the copper-based conductor to which ultrasonic waves, which will be described later, are applied, and the ultrasonic bonding portion 30 is formed together with the aluminum-based conductor exposure portion 22 by the ultrasonic waves. The length of the stripped insulation coating is not particularly limited as long as the copper-based conductor exposure portion 12 has a sufficient length to be ultrasonically joined to the aluminum-based conductor exposure portion 22, and may be appropriately set according to the range of the region to be joined to the corresponding aluminum-based conductor exposure portion 22. The length of the copper-based conductor exposed portion 12, i.e., the length of the stripped insulating coating, is, for example, preferably 5 to 25mm, and more preferably 10 to 20 mm.
(aluminum conductor-coated electric wire)
The aluminum-based covered electric wire 20 used in the present invention has an aluminum-based conductor covering portion 21 in which an aluminum-based conductor is covered with an insulating coating, and an aluminum-based conductor exposing portion 22 in which a part of the insulating coating is stripped by a predetermined length to expose the aluminum-based conductor. The aluminum-based covered electric wire 20 may be, for example, 1 covered electric wire in which an aluminum-based conductor formed by bundling a plurality of strands made of an aluminum-based material is covered with an insulating coating, or may be a plurality of covered electric wires in which such covered electric wires are bundled. The aluminum-based conductor is preferably formed by twisting a strand so as to have a predetermined cross-sectional area, but is not limited to this form and may be formed of a single wire. The wire diameter and number of wires constituting the aluminum-based conductor are not particularly limited, but for example, the wire diameter of the wire is preferably in the range of 0.05 to 1mm, and the number of wires is preferably in the range of 7 to 90.
The aluminum conductor is not particularly limited, and aluminum alloys such as pure aluminum (Al), aluminum-manganese alloys (Al — Mn alloys), aluminum-magnesium alloys (Al — Mg alloys), aluminum-magnesium-silicon alloys (Al — Mg — Si alloys), aluminum-zinc-magnesium alloys (Al-Zn-Mg alloys), and aluminum-copper-magnesium alloys (Al — Cu-Mg alloys) can be used. From the viewpoint of imparting higher strength, an aluminum alloy is preferable.
As such aluminum or aluminum alloy, for example, JIS H4100: pure aluminum of alloy No. 1050, 1060, 1070, 1100 or 1200 in 2015 standard, Al — Mn-based alloy of alloy No. 3003 or 3203, Al — Mg-based alloy of alloy No. 5052, 5454, 5083 or 5086, Al — Mg-Si-based alloy of alloy No. 6101, 6N01, 6005A, 6060, 6061, 6063 or 6082, Al — Zn-Mg-based alloy of alloy No. 7003, 7N01, 7005, 7020, 7050 or 7075, Al — Cu-Mg-based alloy of alloy No. 2014, 2014A, 2017A or 2024.
The insulating coating is not particularly limited as long as it is a material having insulating properties, and examples thereof include a halogen-based resin containing polyvinyl chloride, crosslinked polyvinyl chloride, chloroprene rubber, or the like as a main component, and a halogen-free resin containing polyethylene, crosslinked polyethylene, ethylene-propylene rubber, silicone rubber, polyester, or the like as a main component, and particularly a polyvinyl chloride resin is used as a resin material constituting the insulating coating. Further, additives such as a plasticizer and a flame retardant may be contained in these resin materials as needed.
The aluminum conductor coating portion 21 is a portion of the coated electric wire 1 in which the aluminum conductor is covered with the insulating coating, and the aluminum conductor is covered with the insulating coating without exposing the aluminum conductor. The aluminum conductor coating portion 21 is the first portion of the aluminum conductor that is not affected by the ultrasonic waves described below.
The aluminum conductor exposure portion 22 is a portion where the aluminum conductor is exposed by peeling a part of the insulating coating by a predetermined length. The aluminum conductor exposed portion 22 is a portion of an aluminum conductor to which ultrasonic waves, which will be described later, are applied, and the ultrasonic bonding portion 30 is formed together with the copper conductor exposed portion 12 by the ultrasonic waves. The length of the stripped insulation coating is not particularly limited as long as the aluminum-based conductor exposure portion 22 has a sufficient length to be joined to the copper-based conductor exposure portion 12, and may be appropriately set according to the range of the region to be joined to the corresponding copper-based conductor exposure portion 12. The length of the aluminum conductor exposed portion 22, i.e., the length of the stripped insulation, is, for example, preferably 5 to 25mm, and more preferably 10 to 20 mm.
(ultrasonic bonding part)
The wire connection structure 10 of the present invention has an ultrasonic bonding portion 30 formed by a copper-based conductor exposure portion 12 and an aluminum-based conductor exposure portion 22. The ultrasonic bonding part 30 may be integrally formed by further providing a joint pipe 50 on the outer peripheral side of the conductor laminated portion where the copper-based conductor exposure part 12 and the aluminum-based conductor exposure part 22 overlap. Fig. 2 shows a cross-sectional photograph of the wire connection structure having the ultrasonic bonding part 30, the ultrasonic bonding part 30 having the adapter tube 50 on the outer peripheral side of the conductor laminated portion.
The main feature of the configuration of the present invention is to optimize the properties of the joining interface of the ultrasonic joining part 30 formed by ultrasonic joining, and more specifically, to satisfy the relational expression of (x/L) × 100 ≦ 10% when the total contact length, which is the total length of the portion where the copper-based conductor exposed part 12 and the aluminum-based conductor exposed part 22 are in contact with (joined), and the total length of the outline line of the space S formed by the portion where the copper-based conductor exposed part 12 and the aluminum-based conductor exposed part 22 are separated from each other is taken as L, and the total length of the outline line of the space S in the cross-sectional view of the ultrasonic joining part 30 is taken as x, whereby an increase in resistance due to crevice corrosion and a decrease in the joining strength (tensile strength) can be effectively suppressed.
Here, the reason why the total x of the total contact length L and the outline length of the space satisfies the relational expression of (x/L) × 100 ≦ 10% is that: if the value of (x/L) × 100 is greater than 10%, the portion of the copper-based conductor exposed portion 12 and the aluminum-based conductor exposed portion 22 present at the joint interface of the ultrasonic joint 30 that is separated increases, the number or volume of the spaces that cause the occurrence of the gap corrosion increases, and the resistance increases or the joint strength (pull strength) decreases significantly due to the gap corrosion.
Fig. 3 is a line view showing the ultrasonic bonding part of fig. 2, fig. 4 is a two-dot chain line showing the ultrasonic bonding part of fig. 3 in an enlarged manner, and solid lines showing the portions of the aluminum-based conductor exposed portion and the copper-based conductor exposed portion which are in contact with each other (bonded to each other) at the bonding interface, fig. 5 is a two-dot chain line showing the ultrasonic bonding part of fig. 3 in an enlarged manner, and solid lines showing the space S (3 in fig. 5) formed by the portions of the aluminum-based conductor exposed portion and the copper-based conductor exposed portion which are separated from each other at the bonding interface, and fig. 6 is a view for explaining a method of measuring the total x of the total contact length L of the portions of contact shown in fig. 4 and the outline length of the space S shown in fig. 5.
Here, the "total contact length L" is the total of the lengths of the portions of the aluminum-based conductor exposed portion 22 and the copper-based conductor exposed portion 12 that are in contact with (joined to) the aluminum-based conductor exposed portion 22, which are present at the joint interface between the aluminum-based conductor exposed portion 22 and the copper-based conductor exposed portion 12 in the cross-sectional view of the ultrasonic joint 30, and specifically represents the total of the lengths of the solid lines shown in fig. 4.
The "total x of the contour line lengths of the spaces" is the total of the contour line lengths of the spaces S formed by the portions where the copper-based conductor exposed portions 12 and the aluminum-based conductor exposed portions 22 are separated from each other, which are present at the joining interface between the aluminum-based conductor exposed portions 22 and the copper-based conductor exposed portions 12 in the cross-sectional view of the ultrasonic joining portion 30, and specifically, when the space S is present at only 1 position, the total of the contour line lengths measured in the space S is shown, and when there are a plurality of spaces S (3 positions in fig. 5) as shown by a solid line in fig. 5, the total of the contour line lengths measured in each of the plurality of spaces S is shown.
The total contact length L and the total x of the contour line lengths in the space are measured by the following method: a method of imaging a cross section of the ultrasonic bonding part 30 with an optical microscope or an electron microscope and approximating the extension shape of the bonding interface (shown by a solid line in fig. 6) as much as possible from the imaged image or photograph is, for example, a method of connecting a plurality of straight lines having a length of 10 μm or less (for example, 10 μm) in a line pattern as shown in fig. 6.
In the electric wire connecting structure of the present invention, the difference in tensile strength between the copper-based conductor and the aluminum-based conductor is preferably 100MPa or more. Thus, one of the copper-based conductor exposure portion 12 and the aluminum-based conductor exposure portion 22 (for example, the aluminum-based conductor exposure portion 22) can be made of a material that is more easily deformed than the other conductor exposure portion (for example, the copper-based conductor exposure portion 12), and therefore by combining these conductors, the exposed portion of the one conductor is relatively easily collapsed to a large extent by a pressure force at the time of ultrasonic bonding, in a non-junction (non-contact) space S which is easily formed between the copper-based conductor exposure portion 12 and the aluminum-based conductor exposure portion 22 constituting the junction interface, one conductor exposed portion fills the space S (gap) by plastic deformation or melting, as a result, an ultrasonic bonding portion having a sound bonding interface can be formed, and an increase in electric resistance and a decrease in bonding strength (pull strength) due to the gap corrosion can be further effectively suppressed.
In the measurement of the tensile strength, 3 pieces of the steel sheet were measured in accordance with JIS Z2241, and the average value was obtained.
In the electric wire connecting structure of the present invention, if the difference in tensile strength between the copper-based conductor and the aluminum-based conductor is 100MPa or more, the tensile strength may be higher in the aluminum-based conductor than in the copper-based conductor, or conversely, the tensile strength may be higher in the copper-based conductor than in the aluminum-based conductor, and therefore, the combination of the copper-based conductor and the aluminum-based conductor may be appropriately selected depending on the application and the like.
(method of manufacturing electric wire connection Structure)
Next, a method for manufacturing the wire connecting structure 1 of the present invention will be described. The method for manufacturing the wire connection structure 1 of the present invention mainly includes at least: the method for manufacturing the electric wire includes the steps of preparing the copper-based conductor-coated electric wire 10 and the aluminum-based conductor-coated electric wire 20, forming a copper-based conductor exposed portion and an aluminum-based conductor exposed portion, and ultrasonically bonding the copper-based conductor exposed portion and the aluminum-based conductor exposed portion to form an ultrasonic bonding portion.
(step of preparing coated electric wires)
First, a copper-based conductor-coated electric wire 10 having a copper-based conductor coating portion 11 in which a copper-based conductor is covered with an insulating coating and an aluminum-based conductor-coated electric wire 20 having an aluminum-based conductor coating portion 21 in which an aluminum-based conductor is covered with an insulating coating are prepared. The above materials can be used for the copper-based conductor and the insulating coating constituting the copper-based conductor-coated electric wire 10 and the aluminum-based conductor and the insulating coating constituting the aluminum-based coated electric wire 20, respectively, and the insulating coating is preferably polyvinyl chloride resin. The copper-based conductor is not particularly limited, and is preferably a copper-based conductor formed by twisting and bundling a plurality of strands made of a copper-based material. For example, a size (thickness) of 0.13 obtained by twisting and binding 7 copper-based wires can be usedsq(0.13mm
2) The copper-based conductor of (1). The aluminum conductor is not particularly limited, and is preferably an aluminum conductor formed by twisting and bundling a plurality of strands made of an aluminum material. For example, a size (thickness) of 0.75sq (0.75 mm) obtained by twisting and binding 7 aluminum wires can be used
2) The aluminum-based conductor of (2).
(step of Forming exposed portions of respective conductors)
Next, the copper-based conductor-coated electric wire and the aluminum-based conductor-coated electric wire are formed with a copper-based conductor exposed portion 12 and an aluminum-based conductor exposed portion 22, respectively, which are exposed by peeling a part of the insulation coating by a predetermined length. The method of peeling the insulation coating is not particularly limited, and a tool or a device such as a wire stripper can be used. The length of the stripped insulation coating is suitably designed according to the range of the ultrasonic-bonded region of the conductor exposure portions 12 and 22, respectively, and is preferably 5 to 25mm, and particularly preferably 10 to 25 mm.
(step of Forming ultrasonic Joint)
The ultrasonic bonding is further performed in a state where the copper-based conductor exposure portion 12 and the aluminum-based conductor exposure portion 22 are formed to overlap each other, thereby forming an ultrasonic bonding portion 30. The ultrasonic bonding part 30 may be formed by inserting the outer peripheral side of the conductor laminated portion formed by overlapping the copper-based conductor exposure part 12 and the aluminum-based conductor exposure part 22 into the interior of the adapter tube 50, and then performing ultrasonic bonding while applying pressure from the outer surface side of the adapter tube 50.
In addition, regarding the overlapping of the copper-based conductor exposure portion 12 and the aluminum-based conductor exposure portion 22, the wire harness constituting the copper-based conductor exposure portion 12 or the wire harness constituting the aluminum-based conductor exposure portion 22 may be joined in advance, and then the joined conductor exposure portions 12 and 22 may be overlapped with each other.
The ultrasonic bonding may be performed by: in a state where the copper-based conductor exposure portion 12 and the aluminum-based conductor exposure portion 22 are overlapped, ultrasonic vibration parallel to the bonding surface 33 of the copper-based conductor exposure portion 12 and the aluminum-based conductor exposure portion 22 is applied while applying a pressing force in the vertical direction. It is known that, in general, aluminum instantaneously forms a tough oxide film on the surface when it comes into contact with oxygen in the air, and that the metal surface may be contaminated with substances such as oil and dust. The interfaces of the copper-based conductor exposed portion 12 and the aluminum-based conductor exposed portion 22 rub against each other by friction due to ultrasonic vibration, thereby removing the oxide film or the deposit on the joint surface 33 and causing active metal molecules to appear on the clean joint surface. When ultrasonic vibration is further applied, the movement of the metal atoms is activated by heating due to frictional heat, and the movement of the metal atoms due to diffusion occurs. Strong attraction is generated between the metal members, and the copper-based metal of the copper-based conductor exposure portion 12 and the aluminum-based metal of the aluminum-based conductor exposure portion 22 are bonded in a solid-phase state.
Since the copper-based metal of the copper-based conductor exposure portion 12 and the aluminum-based metal of the aluminum-based conductor exposure portion 22 are bonded in a solid phase by such ultrasonic bonding, the temperatures at which the metals are melted with each other are not increased, and the bonding can be performed at a relatively low temperature (generally, about 35 to 50% of the melting temperature of the base metal). On the other hand, if ultrasonic vibration is applied in parallel to the joint surface 33 between the copper-based conductor exposed portion 12 and the aluminum-based conductor exposed portion 22, microscopic shear deformation due to the ultrasonic vibration occurs, and thereby the ultrasonic joint 30 composed of the copper-based conductor exposed portion 12 and the aluminum-based conductor exposed portion 22 is formed.
Fig. 7 is a schematic view for explaining a process of forming an ultrasonic bonding part 30 having a bonding surface 33 by overlapping the copper-based conductor-coated electric wire 10 and the aluminum-based conductor-coated electric wire 22 with each other using an ultrasonic bonding apparatus 40 and then ultrasonically bonding the interface between the copper-based conductor exposed part 22 and the aluminum-based conductor exposed part 12 in this state.
As shown in fig. 7, for example, the ultrasonic bonding apparatus 40 arranges the copper-based conductor exposed portion 12 and the aluminum-based conductor exposed portion 22 in an overlapped state between the pressing surface of the horn 41 and the pressing surface of the anvil 42, and holds the overlapped copper-based conductor exposed portion 12 and aluminum-based conductor exposed portion 22 from the vertical direction by the horn 41 and the anvil 42, and arranges work holding jigs (slide jaws) 43 on both left and right sides to hold the shape in the overlapped state without deforming. Further, the ultrasonic bonding apparatus 40 can perform ultrasonic bonding by: ultrasonic vibration vibrating in the longitudinal direction X (arrow a1 in fig. 7) is emitted by the horn 41, and pressing is performed by pressing in the pressing direction Z (arrow a2 in fig. 7) by the anvil 42. The energy of the ultrasonic waves to be applied is not particularly limited, but is preferably 100 to 800Ws (J), more preferably 200 to 700 Ws. The compression ratio of the ultrasonic bonding part is preferably in the range of 20 to 80%. Here, the "compression ratio" is a value obtained by dividing the reduction amount of the cross-sectional area before compression by the cross-sectional area before compression, and multiplying the result by 100.
By operating the ultrasonic bonding apparatus 40 in this manner, the ultrasonic vibration emitted from the bonding head 41 propagates the inside of one conductor exposed portion, in fig. 7, the copper-based conductor exposed portion 12 in the pressing direction Z (arrow a31 in fig. 7), and as a result, propagates the inside of the other conductor exposed portion, in fig. 7, the aluminum-based conductor exposed portion 22 in the pressing direction Z (arrow a32 in fig. 7) via the interface where the copper-based conductor exposed portion 12 serves as the bonding surface 33, and as a result, the ultrasonic bonding portion 30 is formed. Here, the joint interface of the ultrasonic joint portion satisfies the relational expression of (x/L) × 100 ≦ 10% for the total x of the total contact length L and the contour line length of the space S, whereby an increase in resistance due to the crevice corrosion and a decrease in the joint strength (pull-out strength) can be effectively suppressed.
The above embodiments are merely illustrative of several representative embodiments of the present invention, and various modifications can be made within the scope of the present invention.
[ examples ]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
(examples 1 to 10 and comparative examples 1 to 5)
A copper conductor-coated electric wire 10 was prepared by covering a copper conductor having the composition, tensile strength, and the like shown in table 1 with a polyvinyl chloride insulating film, and an aluminum conductor-coated electric wire 20 was prepared by covering an aluminum conductor having the composition, tensile strength, and the like shown in table 1 with a polyvinyl chloride insulating film. Next, the tip ends of the coated electric wires 10 and 20 are stripped by about 1.5cm by wire strippers to form copper conductor exposed portions 12 in which copper conductors are exposed and aluminum conductor exposed portions 22 in which aluminum conductors are exposed. The copper conductor exposed portion 12 of the formed copper conductor-coated electric wire 10 and the aluminum conductor exposed portion 22 of the aluminum conductor-coated electric wire 20 are overlapped and then set on a receiving stage (a welding head side) of an ultrasonic bonding apparatus (manufactured by Schunk corporation) in an overlapped state. In examples 1 to 3, the copper-based conductor exposure portion 12 and the aluminum-based conductor exposure portion 22 of the aluminum-based conductor-coated electric wire 20 were disposed on the receiving stage (the welding head side) of the ultrasonic bonding apparatus in a state where the adapter tube was disposed on the outer peripheral side of the conductor laminated portion. Thereafter, while the outer surface of the provided conductor laminated portion or the outer surface of the adapter tube was sandwiched between the horn and the anvil, ultrasonic waves were applied according to the bonding conditions shown in table 1 while applying pressure in the vertical direction, and an integrated ultrasonic bonding portion was formed by ultrasonic bonding. The ultrasonic bonding portions thus obtained were subjected to a corrosion test, the electric resistance and the pull-out strength before and after the corrosion test were measured, the rate of increase in the electric resistance and the rate of decrease in the pull-out strength after the corrosion test were calculated, and the corrosion resistance was comprehensively evaluated based on these calculated values.
(evaluation method)
< measurement of the sum x of the total contact length L and the contour line length of the space >
The total x of the total contact length L and the empty contour length can be measured by the following method: a method of imaging a cross section of the ultrasonic bonding part 30 with an optical microscope or an electron microscope and approximating the extension shape of the bonding interface (shown by a solid line in fig. 6) as much as possible from the imaged image or photograph is, for example, a method of connecting a plurality of straight lines having a length of 10 μm or less (for example, 10 μm) in a line pattern as shown in fig. 6.
< Corrosion test >
Corrosion test using JIS Z2371: 2015 by the salt spray test method. The test conditions are as follows.
[ test conditions ]
Test piece size: 200mm (ultrasonic joint + wire)
Saline solution: neutral salt water
Test temperature: 35 deg.C
·pH：7
Pressure of compressed air: 0.1MPa
Test time: 96h
< measurement of resistance >
The electric resistance of the test piece before the corrosion test and the test piece after the corrosion test were measured by a circuit element measuring instrument (product name: 3560AC m Ω hitter) manufactured by japanese electrical machinery corporation, with respect to one of the electrode attached to the copper conductor of the copper conductor-coated wire and the other electrode attached to the aluminum conductor of the aluminum conductor-coated wire, and the ratio of increase in the electric resistance of the test piece after the corrosion test as compared with the electric resistance of the test piece before the corrosion test (increase rate (%)) was determined.
< measurement of tensile Strength >
The pull strength was measured by fixing the ultrasonic bonding portion and the wire portion to the chuck with respect to the test piece before the corrosion test and the test piece after the corrosion test. The rate of decrease (decrease rate (%)) of the pull strength of the test piece after the corrosion test as compared with the pull strength of the test piece before the corrosion test was determined.
The evaluation results are shown in table 2.
< comprehensive evaluation >
The overall evaluation was made by assuming that the rate of increase in resistance and the rate of decrease in pull-out strength after the corrosion test were both less than 10% as "◎", the rate of increase in resistance and the rate of decrease in pull-out strength were both less than 50% and at least 10% or more as "○", and the rate of increase in resistance and at least 50% or more of the rate of decrease in pull-out strength were "x", and in this example, "◎" and "○" were defined as pass levels.
[ Table 1]
[ Table 2]
From the evaluation results shown in table 2, it is found that: the wire connection structures of examples 1 to 10 each suppressed the increase in resistance to 19% or less after the corrosion test, and also suppressed the decrease in the pull-out strength to 15% or less, and were excellent in corrosion resistance. In contrast, the wire connection structures of comparative examples 1 and 2 were not completely joined, and the joint portion of the wire connection structure of comparative example 4 was broken, so that a sound ultrasonic joint portion could not be formed. In both of the wire connection structures of comparative examples 3 and 5, the resistance increase rate was 320% or more and the pull-out strength decrease rate was 50% or more after the corrosion test, and the corrosion resistance was poor.
Industrial applicability of the invention
The wire connection structure of the present invention is excellent in corrosion resistance by suppressing an increase in electrical resistance and a decrease in bonding strength (pull strength) due to crevice corrosion, and can stably form a sound ultrasonic bonding portion, and therefore, the wire connection structure can be applied to connectors of automotive harnesses and the like, and can be used in various mechanical devices and the like requiring wiring between electronic devices and a plurality of power lines, and is expected to be applied to various fields.
Description of the symbols
1: electric wire connection structure
10: copper conductor coated electric wire
11: copper-based conductor coating portion
12: copper-based conductor exposed portion
20: aluminum conductor-coated electric wire
21: aluminum conductor coating
22: aluminum conductor exposed part
30: ultrasonic bonding part
33: joint surface
40: ultrasonic bonding apparatus
41: welding head (or sound guide bar)
42: anvil block
43: work holding clamp (sliding jaw)
50: connecting pipe
Claims (4)
1. An electric wire connection structure body having:
1 or more copper-based conductor-coated electric wires each having a copper-based conductor-coated portion in which a copper-based conductor made of copper or a copper alloy is coated with an insulating coating, and a copper-based conductor-exposed portion in which a part of the insulating coating is stripped to a predetermined length to expose the copper-based conductor; and
1 or more aluminum-based conductor-coated electric wires each having an aluminum-based conductor-coated portion in which an aluminum-based conductor made of aluminum or an aluminum alloy is coated with an insulating coating, and an aluminum-based conductor-exposed portion in which a part of the insulating coating is stripped off by a predetermined length to expose the aluminum-based conductor,
a joint portion is formed at a conductor laminated portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are overlapped, and the electric wire connection structure is characterized in that,
the joint interface of the joint portion is formed such that, in a cross-sectional view,
the aluminum conductor-coated electric wire is melted and fills the gap of the copper conductor-coated electric wire.
2. An electric wire connection structure body having:
1 or more copper-based conductor-coated electric wires each having a copper-based conductor-coated portion in which a copper-based conductor made of copper or a copper alloy is coated with an insulating coating, and a copper-based conductor-exposed portion in which a part of the insulating coating is stripped to a predetermined length to expose the copper-based conductor;
1 or more aluminum-based conductor-coated electric wires each having an aluminum-based conductor-coated portion in which an aluminum-based conductor made of aluminum or an aluminum alloy is coated with an insulating coating, and an aluminum-based conductor-exposed portion in which a part of the insulating coating is stripped off by a predetermined length to expose the aluminum-based conductor,
an ultrasonic joint is formed at a conductor laminated portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion overlap each other, and the electric wire connection structure is characterized in that,
in a cross-sectional view of the joining interface of the ultrasonic joining portion, when a total contact length, which is a total length of the portions where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are in contact with each other, is L, and a total length of a contour line of a space formed in a portion where the copper-based conductor exposed portion and the aluminum-based conductor exposed portion are separated from each other is x, the following relational expression is satisfied:
(x/L)×100≤10％。
3. the electric wire connection structure according to claim 1 or 2, wherein the difference in tensile strength between the copper-based conductor and the aluminum-based conductor is 100MPa or more.
4. The wire connection structure according to any one of claims 1 to 3, further comprising a joint pipe in which an ultrasonic joint is formed on an outer peripheral side of the conductor laminated portion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017121107 | 2017-06-21 | ||
| JP2017-121107 | 2017-06-21 | ||
| PCT/JP2018/022056 WO2018235637A1 (en) | 2017-06-21 | 2018-06-08 | Wire connection structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110785894A true CN110785894A (en) | 2020-02-11 |
| CN110785894B CN110785894B (en) | 2020-12-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201880042148.8A Active CN110785894B (en) | 2017-06-21 | 2018-06-08 | Electric wire connection structure |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US11387581B2 (en) |
| EP (1) | EP3644443A4 (en) |
| JP (1) | JP6989605B2 (en) |
| CN (1) | CN110785894B (en) |
| WO (1) | WO2018235637A1 (en) |
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| CN113990562A (en) * | 2020-07-27 | 2022-01-28 | 住友电装株式会社 | Terminal structure and sleeve of shielded wire |
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| CN113593748B (en) * | 2021-05-27 | 2023-10-10 | 福建明锐新材料科技有限公司 | Alloy copper wire and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3644443A4 (en) | 2021-04-07 |
| WO2018235637A1 (en) | 2018-12-27 |
| CN110785894B (en) | 2020-12-29 |
| EP3644443A1 (en) | 2020-04-29 |
| US11387581B2 (en) | 2022-07-12 |
| JPWO2018235637A1 (en) | 2020-04-23 |
| US20200136277A1 (en) | 2020-04-30 |
| JP6989605B2 (en) | 2022-01-05 |
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